JPS63287768A - 1-aryl-3-halogenoalkyl-4-halogeno-pyrazole - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel l-aryl-3-halogenoalkyl-
4-Halogeno-pyrazoles, their preparation and their use as insecticides.

It has already been disclosed that various 1-aryl-pyrazole derivatives have pesticidal properties. Thus, for example 4
Certain acid amides of -cyano-5-amino-1-(2,4,6-drichlorophenyl)-pyrazole have a herbicidal action (DE-A-3226.513). 1-Arylpyrazole derivatives substituted in the 4-position by CN and in the 5-position by halogen also have herbicidal activity (DE-A-3.520.329). ■-Phenyl-3-trifluoromethyl-4-fluoro-pyrazole is known from research on the reaction of polyhalogenated arenes, published in the Journal of the Chemical Society (J.

Chem, Soc, ) 1982.2207).

However, nothing has been disclosed so far regarding the insecticidal effects of these compounds.

Formula (I) R' (wherein R1 represents halogenoalkyl, Hal represents halogen, and R2, R3, R4, R5 and R6, in each case independently of each other, represent hydrogen, halogen, cyano, nitro , alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxycarbonyl or -(X). -R7 group, where X is oxygen, sulfur, sulfinyl or sulfonyl, and n is the number 0 or l. , and R7 represents halogenoalkyl, provided that when R2-R6 simultaneously represent hydrogen, R1 represents trifluoromethyl and Hal represents no fluorine). A 3-halogenoalkyl-4-halogeno-pyrazole was found.

Furthermore, this novel 1-aryl-3-halogenoalkyl-4-halogeno-pyrazole of formula (1,) is a) of formula (II) (wherein R1 represents halogenoalkyl and Hal represents halogen). , and R is alkyl) with an arylhydrazine of the formula (I[[) in which R2-R6 have the meanings given above, if appropriate. or b) an N-aryl hydrazide halide of formula (IV) in which R1-R6 and Hal have the meanings given above in a diluent, or b) an N-aryl hydrazide halide of formula (V) Hal
-CH=CH-Hal (V) (wherein H
al has the meaning given above), if appropriate in a diluent and if appropriate in the presence of an acid-binding agent, or C) with an alkene of formula (Vl) R″″ (formula 1-aryl-3-halogenoalkyl-pyrazole in which RI-R6 has the above meaning is reacted with a halogenating agent such as fluorine, chlorine or bromine, if appropriate in a diluent. , or d) N-arylcytonone of the formula (■) (in the formula, R2-R6 has the above-mentioned meaning) is converted into N-arylcytonone of the formula (■) R'-C=C-Hal (■) (in the formula , R'
and Hat has the meaning given above), if appropriate in a diluent.

Finally, it has been found that this new l-aryl-3-halogenoalkyl-4-halogeno-pyrazole has very good insecticidal action.

Surprisingly, the 1-aryl-3-halogenoalkyl-4-halogeno-pyrazoles of the general formula (I) according to the invention are the pyrazole derivatives known from the prior art,
The chemically similar compound 4-cyano-5
-Propionylamino-1-(2,4,64-lichlorophenyl)-pyrazole has significantly better insecticidal action.

Formula (I) provides a general definition of 1-aryl-3-halogenoalkyl-4-halogeno-pyrazoles according to the invention. Preferred compounds of formula (I) are those in which R1 is straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, and Hal is fluorine, chlorine, bromine or iodine; and R2, R3, R4, R5 and R6 are each independently hydrogen, halogen, cyano, nitro, alkyl, alkylthio, halogenoalkyl, halogenoalkoxy,
halogenoalkylthio, alkylsulfinyl, alkylsulfonyl, halogenoalkylsulfinyl, halogenoalkylsulfonyl or alkoxycarbonyl, in each case from 1 to 4 carbon atoms in the individual alkyl moiety;
and, if appropriate, with 1 to 9 identical or different halogen atoms, where R2-R6
At the same time, R1 does not yield trifluoromethyl and Hal does not yield fluorine. Particularly preferred compounds of formula (I) are those in which R1 is trifluoromethyl, dichlorofluoromethyl,
Hat produces fluorine, chlorine or bromine, and R2, R3 , R4, R5 and R6 are in each case independently of each other hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-1i-
15- or t-butyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyltrifluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluoromethinopentafluoroethoxy, trifluorochloroethyl, trifluoroethyl, trifluorodichloroethyl , difluorochloroethyl or -X-R7 group, where X is oxygen, sulfur, sulfinyl or sulfonyl, and R7 is trifluoromethyl, dichlorofluoromethyl,
Difluorochloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorochloroethyl, trichloromethyl or trifluorodichloroethyl, where R2-R6 simultaneously Then R1 is a compound that does not contain trifluoromethyl and Hal does not contain fluorine.

In addition to the compounds mentioned in the Preparation Examples, the following formula % 4-halogeno-pyrazoles may be mentioned individually: R' Hal R2R3R'R'
R'CFs CI CI HCF3
HFeF2 CIF F
CFs F FeF2 B
r CI H5O2CF3 HClCF3
Br CI HCF3 HFCFs
F CI HCI H
CICF 3 F F F
CF3FFeF2CI
CI H0CF3 HClCF3
CI CI HCFs HHCF
3 B r CI CI CF 3
HCICF, F, CI
CI CF3 HCIC2F s
CI CI HCF 3 HC
IC2F s B r CI HCF
s HCIC, F, CI F
F CF3 F CF
s F CI HCFs
HFC2F5 F CI HCFs
HFc2Fs F CI
HCF, HCIC2F5 CI
CI H5o2CF3 HCIC3Fy C
I CI HCFs HCIC3F
'? F CI HCFs
HCIC,F7 Br CI HCF,
HCIC3F, CI CI
HSo, CF3 HCIC3F? F
CI HCI HCIC4FB
CI CI HCF3 HCIC
Cl□FCI CI HCFs H
CICFzCICI CI HCF,
HClC3F7 F CI HCF,
HFCHF2 CI CI HCF
, HClCHF2 CI CI
H5O2CFs HC1 If, for example, 3-bromo-4-ethoxy-1゜1.14lifluoro-budo-3-
If en-2-one and 2,6-dichloro-4-trifluoromethyl-phenyl-hydrazine are used as starting materials, the process of reaction process (a) according to the invention can occur according to the following formula: , for example l;t''N-(2-chloro-6-fluoro-
If 1-trifluoro-methylphenyl)-trifluoroacetohydrazide bromide and 1,2-dichloroethylene are used as starting materials, the course of the reaction process (b) according to the invention can occur according to the following formula: CF.

If, for example, 1-(2,6-dichloro-4-trifluoromethoxyphenyl)-3-trifluoromethylpyrazole and fluorine are used as starting materials, the process of reaction process (c) according to the invention can be carried out according to the following equation: can occur: if, for example, N-(2,6-dichloro-4
-trifluoromethylphenyl)-cytonone and tetrafluoropropyne as starting materials, the course of the reaction process (d) according to the invention can occur according to the following formula: CF.

The halogen-substituted acyl enol ethers of the formula (U) in which R1, Hal and R have the meanings given above, which are necessary as starting materials for carrying out the process (a) according to the invention, are novel. and is the subject of a parallel application. They are, for example, acyl enol ethers of formula (II) (wherein R1 and R have the meanings given above) with a halogenating agent at temperatures ranging from -70°C to +80°C.
°C, if appropriate in the presence of a diluent, and the resulting halogenated product of formula (X), if appropriate isolated, and between -20°C and +100°C. It is obtained by denogenation at a temperature of .

The arylhydrazines of formula (III) required as starting materials are known (for example, GB 154.115, GB 187.285, GB 34945).

Formula (IV) gives a general definition of the N-arylhydrazide halides required as starting materials for carrying out process (b) according to the invention. In the formula, R1-R6 and H
al preferably represents the substituents already mentioned as preferred for these substituents in connection with the description of the compounds of formula (1) according to the invention.

Some N-aryl hydrazide halides of formula (IV) are known (Chem.

Lett,) 1982, 543; Journal of
Heterocyclic chemistry (J, Hete
r-ocycle, Chem,) 22,565 (1
985); British Patent No. 1,019). They include, for example, arylhydrazines of formula (III), arylhydrazines of formula (XI)
or its semiacetal or hydrate (XI[) (wherein R1 has the above meaning and R8 is hydrogen or alkyl) to form a compound of the formula (XIII) (wherein R1 has the above meaning and R8 is hydrogen or alkyl). . It is obtained by reaction in the presence of a diluent such as formamide or acetic acid at a temperature of -30° to 100°C.

Halogenoalkyl aldehydes of formula (XI) and their hydrates or acetals of formula (XI[) are known compounds (Journal of the American Chemical Society (J, Amer.).

Chem, Soc, ) 76.300, (1954)
).

The alkenes of the formula (V) required as starting compounds for carrying out the process (b) according to the invention are known.

The l-aryl-3-halogenoalkyl-pyrazoles required as starting compounds for carrying out process (c) according to the invention are compounds known in organic chemistry (eg Chemical Letters, 1982.543).

The N-arylcitonones required as starting materials for carrying out process (d) according to the invention can be obtained analogously to known methods (Organic Synthesis, Org, 5
ynth, ) 45.96 (1965)).

Suitable diluents for carrying out process (a) according to the invention are organic solvents. Polar organic solvents are preferably used, such as glacial acetic acid, ethanol, n-butanol, dimethylformamide or ethylene glycol monomethyl ether. In order to simplify the ring closure of the pyrazole formation, acid catalysts such as sulfuric acid, hydrochloric acid or triple oroacetic acid can optionally be added, which are preferably used in small amounts.

When carrying out process (a) according to the invention, the reaction temperature can be varied within a relatively wide range.

Generally, the process is carried out at a temperature between 0°C and the boiling point of the optionally added diluent, preferably between +20°C and 120°C.

To carry out the method (a) according to the invention, the formula (I
1.0 to 2.0 mol, preferably 1.0 to 2.0 mol of arylhydrazine of formula (I) per mol of acyl vinyl ether of I).
0 to 1.4 mol is used.

The reaction is carried out and monitored and the reaction products are worked up and isolated in conventional manner.

A particular variant of process (a) according to the invention consists in dehalogenating the halogenated product of formula (X) in the presence of an arylhydrazine of formula (II[).

Suitable diluents for carrying out process (b) according to the invention are inert organic solvents.

They are in particular aliphatic or aromatic optionally halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; ethers such as diethyl ether, dioxane , tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; nitriles such as acetonitrile or propionitrile; amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, or esters such as ethyl acetate. .

Process (b) according to the invention is preferably carried out in the presence of a suitable acid-binding agent. All customary inorganic or organic bases are suitable as such. Tertiary amines such as triethylamine, N,N-dimethylaniline, pyridine, diazabicyclooctane (DABCO)
, diazabicyclononene (D B N) or diazabicycloundecene (D B U) are preferably used.

When carrying out process (b) according to the invention, the reaction temperature can be varied within a relatively wide range. -23 Generally, the process is carried out at a temperature of -30°C to +150°C, preferably at a temperature of 0° to +100°C.

To carry out the process (b) according to the invention, from 1.0 to 20.0 mol, preferably from 1.0 to 5.0 mol, preferably from 1.0 to 5.0 mol, of an alkene of formula (V) per % formula % and if appropriate Bolic acid-
1.0-20.0 moles of binder, preferably 1.0-2
．． 0 mol is used. The reaction is carried out and monitored and the reaction product of formula (I) is worked up and isolated in conventional manner.

Suitable diluents for carrying out process (c) according to the invention are organic solvents that are inert towards the halogenating agent. For example, tetrachloromethane, fluorochlorohydrocarbons such as trichlorofluoromethane, 1.1.1-1-lifluoro-2,2,2-trichloroethane and 1.1.2-trifluoro-1°2.2-)dichloroethane, Glacial acetic acid, formic acid, trifluoroacetic acid or perfluoroalkanes are suitable.

When carrying out the process (c) according to the invention the reaction temperature is -7
It can be varied within the range of 8°C to +100°C.

Fluorination using elemental fluorine is preferably carried out using elemental fluorine.
C. to +20.degree. C., whereas the chlorination can be carried out at higher temperatures, for example the boiling temperature of tetrachloromethane.

The halogenating agent can be activated by adding a free radical initiator such as azoisobutyronitrile or by UV light.

To carry out the process (c) according to the invention, 1.0 to 3.0 monomers of halogenating agent are preferably used per mole of 1-aryl-3-halogenoalkylpyrazole of formula (Vl), preferably 1.0 to 1.5 mol is used.

The reaction is monitored and carried out and the reaction products are worked up and isolated by known methods.

Suitable diluents for carrying out process (d) according to the invention are inert organic solvents, such as toluene, benzene, xylene or mesitylene.

The reaction temperature when carrying out this method (d) is expressed by the formula (■)
depending on whether the N-arylcytonone is decarboxylated thermally or photochemically.

In the former case a temperature of 100 DEG C. or higher is required, which is determined by the substituents R2 to R6 on the N-arylcytonone. 100 for photochemically induced reactions
Temperatures below 0.degree. C. are sufficient and process (d) is preferably carried out at temperatures in the range -20.degree. C. to 60.degree.

To carry out the method (d) according to the invention, N of the formula (■)
-1.0 to 3.0 mol, preferably 1.0 to 2.0 mol of alkynes of formula (■) are used per mole of arylcytonone. The reaction, monitoring and work-up are carried out in a manner known per se.

The active compounds of formula (I) are suitable for use against animal pests, preferably arthropods and nematodes, which are encountered in agriculture, forestry, the protection of stored products and materials and in the hygiene sector. -a
tode), especially insects and arachnids (arac
suitable for combating hn-4da). They are active against normally sensitive and resistant species and all or some growth stages.

The above-mentioned pests include: those of the order Isopoda, such as Oniscus asellus, A rmadillidium vulgar;
e), and Porcellio power bar (Porcellio
5cabar); Diplopoda (D 1plopoda)
those of, for example, Braniulus gutlatus (B 1
aniulus gutLulatus); members of the order Chilopoda, such as Geophilus ca
rpoh-agus) and Scutige
ra spp, ); S ymphyl
a), such as Scatigerera immaculata (S
cutigerellaimmaculata; those of the order Thysanura, such as Lepisma saccharina (Lepisma 5acchari);
na); Collembola (Colembola);
Example 11 Onychiurus almaras
rus armatus); Orthoptera
era), such as Plata orientalis (B
1atta orientalis), American cockroach (Periplaneta americana)
), Leucophea maderae
macierae), German cockroach (B I
attella germanica), attella germanica)
Acheta domesticus
), Gryllotalpa spp, ), Locustamigratoria
migratorioides), Melanoplus diffe
renti-alis) and Schistoc-erca gregar.
ia); those of the order Dermaptere, such as Forficula auricularia (Forf 1c);
ulaur icu jaria) ; those of the order Termite (l5optera), such as Reticulitermes sp.
p, ); members of the order A noplura, such as Phylloxera bastarix
Vastatrix), Penfigus (P emp
higus 5pp-), and human lice (Pedi
culus humanus corporis)
, Haematopinus spp.
, ) and the wood louse (L inognathus
spp, ); Mallophaga
such as the brown lice (Trichodec).
tes spp,) and Damalinia
ea spp, ); Thripsipales (T hysano
ptera), such as Clybane thistle? (He
rcinothrips femoralis) and Negiazamira? (Thrips tabaci); Heteroptera, such as Eurygaster spp, Dysdercus intermezius
intermedius), Piesma quadrata (
Piesma quadrata), bed bug (Cimex 1ectularius), Rhodnius prolixu (Rhodnius prolixu)
s) and Triatoma spp.
); Homoptera, such as A Ieurodes br.
assicae), cotton whitefly (B emisia)
tabaci), Trialeurodes vaporari
o-rum), cotton aphid (Aphis gos
sypii), radish aphid (B revico
ryne brassicae)
Cryptomyzus ribis, Doralis fabae x,
Doralis pomi, E riosoma lanigeru
m), Hyalopterus aphid
arundinis), wheat aphid (
Macrosiphum avenae), Myzus spp., P horod-on humuli, Rhopalos-iphum p.
adi), Empoasca spp.
), Euscelis bilobatus (Euscelis
bilobatus), black leafhopper (Nepho
tettix cincticeps), Lecanium corni, Saissetia ol.
eae), Laodelphax
5 triatellus), brown planthopper (N 1l)
aparvata lugens), Aonidiella aurantii
, A 5pidiotus
hederae), Pseudococcus (P 5eud
ococcus spp,) and Psyl spp.
la spp, ); - of the order Ptera, such as Pectinophora goss;
ypiella), Bupa-viniarius (Bupa)
lus piniarius), Cheimatobia brumata,
Lithocollitis plancartera (L 1thocoll)
etis blancardel Ia), Hypo-nomeuta padel
la), diamondback moth (Plutella maculi-
pennis), Malacosoma
neustria), and Eupro
ctis chrysorrhoea), Gypsy moth (Lyman-tria spp.), Bucculatrix sulberiella (Bucculatrix t.
Hurberiella), Citrus leafminer moth (Phys
llocnistis citrella), Yaga (
Agrotis spp.), Euxoa
spp, ), Feltia 5pp
-), near insulana (E arias 1
nsulana), Heli-this
spp, ), L aphyg
maexigua), armyworm (Mamestra)
brassicae), Panolis flamea (Pan
olis flammea), Spodoptera communis (Pr.
odenia 1itura), White Spodoptera (S
podoptera spp,), Trichobrusia
Trichoplusia ni, Carpocapsa pomonella = 31- (Carpocapsa pomone I la)
, Pierisspp, Chils spp, Pyra
usta nubilalis), Ephestia kuehniella,
Honey hemlock (Galleria mellonell)
a), Teineola biseriella (T 1neola
bisselliella), Teinea perionella (
T 1nea pellionella), Hofmannophylla bushtospletella
ila pseudo-spretella), Cacoecia podana (Cacoec 1apodana),
Capua reticular-
ana), Christoneura fumifuelana (Chori
st-oneura fumiferana), CIysia ambiguera
lla), Chabamaki (Homonamagnan i)
ma), and Tortorix viridana (Tortri
x viridana); Coleoptera
ra), such as Anobium bunctatum (An
obium punctatum), Rhizopertha dominica,
Bruchidius obtectus
obtectus), bean weevil (Aca
nthoscelides obte-ctus),
Hylotorbes trupes (j(yl+)trupes
bajulus), Agelastica aruni (A gel
asticaaln+), Leptinotarsa decemlin
eater), Phaedon cochleariae (Phaedo
n cochleariae), diabrochi force (D
1abrotica spp,), Psylliodes chrysocephala
cephala), E pi
Lachna varivestis), A tomaria spp., Oryzaephilus suriname
nsis), Anthonomus
spp, ), brown weevil (S 1tophilus
spp, ), Otiohynchus sulcaras (Otio
rrhychus 5ulcatus), cabbage weevil (Cosmopolites 5ordidus)
), Ceuthorr.
Hynchus assimillis), Hypera postica (Dermestes spp,), Trogoderma spp, Anthrenus spp, Atatag enus spp,), Lyctus spp,) , Meligetes
Aeneus
, ptinus spp, Niptus holol
eucus), Semaru leopard beetle (Gibbiu)
m psylloides), and the small-breasted butterfly (T.
ribolium spp,), T enebrio molitor
, click beetle (Agr-4otes 5pp-),
Conoderus spp, Melolontha mel
olon-tha), Amphimallon 5olstitialis
is) and Kometeritra zealansica (Costel
ytra zealandica); Hymenoptera (Hym
enoptera), such as the pine sawfly (D 1
prion spp, ), Hoplo spp.
campaspp, ), Lasius s
pp, ), Monomorium p.
haraonis) and wasp (Vespa s
pp, ); those of the order Diptera (D 1ptera), such as Aedes (Aedes
edes 5pp-), Anophel
es spp, ), CuleXspp, ),
Drosophila melanogaster
melanogaster), house fly (Muscas)
pp, ), Fannia spp.
), black fly Erythrocephala (Calliphor
o erythrocephala), golden fly (Lu
cilia spp, ), Chrys spp.
'omya spp,), Cuterebra
braSl)p,)% Gastrophi
lus spp, ), Hyppobo
sca spp,), S tomoxys
spp, ), sheep fly (Oestrus spp,
), bull flies (Hypoderma spp, ), horseflies (T abanus spp, ), tania (Tan
nia spp,), Keba-c (B 1bio
hortulanus), Oscineella furito (O5c
inella frit), Black Kimba x (P h
orbia spp,), P. orbia spp.
egomyia hyoscyami), Ceratitis capitata
ata), fruit fly D acus o 1e
ae) and Gaganpo pardosa (T 1pula
paludosa); Chiliformes (S 1phonapte
ra), such as those of Xenops rat flea (Xenops
sylla cheopis) and C'e
ratopyllus spp,).

In this case, the active compounds according to the invention can be applied to foliar and soil insects, such as the mustard beetle.
It can be used particularly effectively to control the larvae of (Phuedon cochleariae).

Depending on their particular physical and/or chemical properties, the active compounds can be formulated into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols,
Coating compositions for active compound-impregnated natural and synthetic materials, microcapsules and seeds in polymeric substances, and also formulations for use with fumigation devices such as fumigation cartridges, fumigation cans, fumigation coils and the like, as well as ULV cold fog. and warm fog formulations.

These formulations are prepared in a known manner, for example by combining the active compound with a spreading agent, i.e. a liquid solvent, a pressurized liquefied gas and/or a solid carrier, optionally a surfactant, i.e. an emulsifying agent and/or a dispersing agent.
and/or using foam-forming agents and by mixing. When using water as a spreading agent, organic solvents can also be used as auxiliary solvents, for example. The following are mainly suitable as liquid solvents: aromatic compounds such as xylene, toluene or alkylnaphthalenes,
Chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as mineral oil fractions, alcohols such as butanol or glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl formamide and dimethyl sulfoxide, and water: Spreading agents or carriers for liquefied gases are gaseous at room temperature and pressure. , such as halogenated hydrocarbons and aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as solid carriers, the following are suitable: for example ground natural minerals such as kaolin, Suitable solid carriers for the granules are: clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates: e.g. Crushed and sized natural rocks such as calcite, marble, pumice,
Synthetic particles of sepiolite and dolomite, as well as inorganic and organic flours, and particles of organic materials, such as sawdust, coconut husks, corn cobs and tobacco stalks; as emulsifiers and/or foam formers, the following are suitable: : for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfonates, arylsulfonates and albumin hydrogenation products; dispersions Suitable agents include, for example, lignin-sulfite waste liquor and methylcellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in powder, granular or latex form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids can be used in the formulation. . Other additives can be mineral and vegetable oils.

Inorganic pigments such as iron oxide, titanium oxide and plastic pigments
It is possible to use colorants such as blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and salts of micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.

The active compounds according to the invention can be used in combination with other active compounds, such as insecticides, poison baits, fungicides, acaricides (ac
aricide), nematicides, bactericides and fungicides (fu
ngicide), growth-regulating substances or herbicides.

Pesticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenyluria and substances produced by microorganisms, among others.

391 The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms made from these formulations in mixtures with synergistic agents. A synergist is a compound that increases the action of the active compound; the added synergist need not itself be active.

The active compound content of the use forms prepared from commercially available formulations can vary within a wide range. The active compound concentration of the usage form is between 0°0000001 and 95% active compound.
% by weight, preferably 0.0001-1
Weight%.

The compounds are used in a conventional manner appropriate to the intended use.

Preparation Examples Examples l o2cF3 (Method a) 3-chloro-4-ethoxy-1,l,l-)lifluoro-budo-3-en-2-one 10.1 g (0.05 mol) and 2.6- 15.5 g (0.05 mol) of dichloro-4-trifluoromethylsulfonylphenylhydrazine are heated to 100 DEG C. for 6 hours in 50 ml of glacial acetic acid. After addition of water, the mixture is extracted with dichloromethane, the combined dichloromethane extracts are washed with aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and the filtrate is evaporated. Petroleum ether (boiling range 60
~80 °C) with a melting point of 97
7.1 g (30%) of 4-chloro-1-(2,6-cyclo-4-trifluoromethylsulfonylphenyl)-3-trifluoromethylpyrazole are obtained at ~100°C.

'HNMR (80MH2, CDC13): δ-7,71
s (IH) and 8.13 ppm s (2H).

Example 2 CI (Method b) 11.1 g (0,0
3 mol) and 5.82 g of 1,2-dichloroethylene (
6.7 g (0.066 mol) of triethylamine are added dropwise at 80° C. with stirring to a solution of 0.06 mol) in 5 ml of toluene. The mixture was stirred at 80°C for 5 hours,
Cool and remove the triethylammonium bromide. The solution was evaporated and the residue was chromatographed on silica gel with petroleum ether (boiling range 60-80°C) to give 4-chloro-1-(2,4,6 -trichlorophenyl)-3-
Trifluoromethylpyrazole 1.44g (14%)
give.

'HNMR (80MH2, CDC13): δ-7,50
s (2H) and 7.63 ppm s (I H).

Example 3 (Method a) 50 m of n-pentane (4-ethoxy-111,1 in 2
-trifluorobodo-3-en-2-one 8.5 g (
8.0 mol) of bromine in 50 mQ of n-pentane
g (0.05 mol) are added dropwise at -2000.

The mixture was then stirred for 1 hour at -20°C, the n-pentane was removed by distillation, and 12.3 g (0.05 mol) of 2,6-dichloro-4-trifluoromethylphenylhydrazine in 100 ml of ethanol was dissolved. Added. 2
After refluxing for an hour, the reaction solution is evaporated under water jet vacuum, the residue is taken up in dichloromethane, the solution is washed with water until neutral, dried over sodium sulfate, filtered,
Then, the furnace liquid is evaporated. The residue was chromatographed on silica gel with toluene/petroleum ether (1:1 by volume) to give 4-bromo-1, mp 89-91'O.
(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylpyrazole 8.4g (4
0%) is obtained.

'HNMR (80MHz SCDCIs): δ-7,66
s (IH) and 7.74 ppm s (2H).

Example 4 (Method C) 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylpyrazole3. Og,
Into a suspension of 20 g of aluminum oxide and fluorotrimethane (Frigen R11) 250 + n + 2, 3.8 g (10 mmol) of fluorine in helium
Delivered as a % strength solution at -7800. 78% of the mixture
Stir for a further 30 minutes at °C and warm to 0 °C, separate the phases and evaporate the organic phase. Chromatography using petroleum ether (boiling range 60-80 °C) on silica gel was performed using 1-(2,6-dichloro-4-trifluoromethylphenyl)- This gives 0.22 g of 4-fluoro-3-trifluoromethylpyrazole.

'HNMR (80MHz, CDCl,): δ-7,55
d(IH,J = 4.1 Hz) and 7.75 ppm
s (2H).

The 1-aryl-3-halogenoalkyl-4-halogenopyrazoles of the general formula (I) shown in Table I are obtained in a corresponding manner according to the general instructions for the preparation: Preparation Example 9 of the Starting Compounds 150 mQ of dichloromethane Medium 4-ethoxy-1゜1.1
-trifluorobodo-3-en-2-one 25.59
(0.15 mol) to a solution of dichloromethane 90 m (2
21.0 g (0.degree. 165 mol) of sulfuryl chloride in the solution were added dropwise at 0.degree. C. over a period of 30 minutes with stirring.

The mixture is stirred for a further 3 hours at 0 DEG C. and the solvent and unreacted sulfuryl chloride are substantially removed by distillation under water jet vacuum to give 38.3 g of a pale yellow powder. Configuration 'H-N
As tracked from the MR spectrum (CDC1,) it follows the structure of a mixture of approximately equal amounts of diastereomers of 3°4-dichloro-4-ethoxy-1,1,1-trifluorobutan-2-one.1. 1-1.5.3.5
~4.2.4.75~5.0 and 5.75~5.9pp
m signals in a ratio of 3:2:1:l. The proportion of 3-chloro-4-ethoxy-1,1,14-lifluorobudo-3-en-2-one in the mixture is less than 5%. The diastereomeric mixture can be distilled at 1 Torr to remove traces of solvent without decomposition.

Example 10 3,4-dichloro-4=ethoxy-1,1,1-trifluorobutan-2-one (38
. °C/lO torr, with n=1.4380°' HN MR (CD Cl s ): δ-1,5
5t (3H, J-8Hz), 4.4q (2H) and 8.00 ppm s (lH) J R (CC14)
: VCO=1710cm-'.

Example 11 8°35 g of 4-ethoxy-1,1,1-trifluoro-budo-3-en-2-one in 50 ml of pentane (0
, 05 mol) to bromine 8.0 g (0
, 05 mol) are added dropwise at -20°C with stirring. The mixture was stirred for a further 1 hour at -20°C and then 6.0 g of triethylamine (0,06
mol) in a fed-batch manner. After stirring overnight at 2Q'O, pour the reaction onto ice.

The mixture is acidified using IN hydrochloric acid (pH 4-5) and extracted with petroleum ether. The solution was dried over anhydrous sodium sulfate and evaporated to give 12.1 g of a yellow liquid, which was subjected to fractional evaporation under reduced pressure.

Low point 100-102℃/16 torr, n? t3=l.

4680 3-bromo-4-ethoxy-1,1゜1-)
10.4 g of refluorobodo-3-en-2-one are obtained and crystallized at -30.degree.

'H-NMR (CDCl3): a = 1.51t (
3H, J-8Hz), 4.45g (2H) and 8.
06 ppm s (I H) I R (CC14):
VCO=1710cm-'.

Example 12 Trifluoroacetaldehyde N-(2,6-dichloro-4-trifluoromethylphenyl)-hydrazone 8°12 g (0,0
25 mol) of N-bromosuccinimide to a solution of 4.45
g (0,025 mol) in portions at room temperature,
At this time, an exothermic reaction occurs. The mixture is stirred at room temperature for 3 hours, the dimethylformamide is removed on a rotary evaporator, and 20 ma of petroleum ether are added to the residue. After filtering off the precipitated succinimide with suction, the filtrate is evaporated and subjected to bulb-tube distillation. N-(2,6-dichloro-4
9.26 g (91.7%) of -)-trifluoroacetohydrazide bromide are obtained. Boiling point 1100 (0.05 torr), nV=1.5
10°'H-NMR (80MHz, CDCl, δ value): 8.
56 (bs, l H); 7.74 (s,
2H).

Trifluoroacetaldehyde (N-(2,4,6-)dichlorophenyl) in 3.3 ml of dimethylformamide
- 3.2 g (0,011 mol) of hydrazone and 1.5 g of N-chlorosuccinimide (.

, 011 mol) at room temperature for 3 hours. After evaporating,
Petroleum ether is added to the mixture, which is filtered and evaporated again. Bulb-tube distillation of the residue at 150° O (0.35 torr) gives 3.2 By (89.6%) of N-(2°4.6-trichlorophenyl)-trifluoroacetohydrazide chloride. n back-1,5
49°'H-NMR (80MHz, CDCl1.δ value): 8.
12 (bs, IH); 7.48 (s, 2H).

The N-aryl-halogenoalkyl-hydrazide halides of the general formula (IV) shown in Table 2 below are obtained in a corresponding manner and according to the general instructions for the preparation.

Example 20 Trifluoroacetaldehyde ethyl semiacecool 1
00g (0,69 mol) and 16L of 2,6-dichloro-4-trifluoromethyl-phenylhydrazine 1g
(0.69 mol) is heated to 100° C. for 6 hours. After removing the volatile components, the residue is recrystallized from petroleum ether. 200 g (89%) of trifluoroacetaldehyde N-(2,61chloro-4-trifluoromethylphenyl)-hydrazone with a melting point of 45-46 DEG C. are isolated.

'HN M R (80MHz, CD C1s
, δ value): 8.15 (bs, lH); 7.7
2(s, lH); 7.12(q, IH,
J=3.9Hz).

The halogenoalkyl aldehyde N-arylhydrazones of the general formula (■) shown in Table 3 are obtained in a corresponding manner according to the general instructions for the preparation.

USE EXAMPLES In the following usage examples, the following compounds were used as comparison compounds: I 4-cyano-5-propionylamino-1-(2,4,
6-Trichlorophenyl)-pyrazole (known from German Patent Application No. 3.226.513).

Example A LD. . Test Test animal: Sitoph granaria (Sitop-h
Solvent: Acetone 2 parts by weight of active compound are taken up in 1,000 parts by volume of solvent.

The resulting solution is further diluted with solvent to achieve the desired concentration.

Pipette 2.5 ml of active compound solution into a Petri dish. Place a circular filter paper approximately 9.5 cm in diameter on the bottom of the Petri dish. The Petri dish is left open until the solvent has completely evaporated. The amount of active compound per m' of filter paper varies depending on the concentration of the active compound solution. The test animals are then placed in 25 petri dishes and the dishes are covered with glass lids.

The condition of the test animals is checked 3 days after the start of the experiment. Test the eradication rate %.

In this test, superior effects compared to the conventional technology were found, for example, in Manufacturing Examples (1), (2), (3), (4),
It is produced by the compounds (6) and (7).

Yoshi-Eight LDloo-Test (Granaria granaria (S 1)
tophilus granarius) Human-A (continued) Example B LD+oo test Test animal: German cockroach (B lattella
german 1ca) Solvent: Acetone 2 parts by weight of the active compound are taken up in 1,000 parts by volume of solvent.

The resulting solution is further diluted with a solvent to achieve the desired concentration.

Pipette 2.5 mff of the active compound solution into the Petri dish. Place a circular filter paper approximately 9.5 cm in diameter at the bottom of the Petri dish. The Petri dish is left open until the solvent has completely evaporated. The amount of active compound per m'' of filter paper varies depending on the concentration of the active compound solution. The 10 test animals are then placed in a Petri dish and the Petri dish is covered with a glass lid.

The condition of the test animals is checked 3 days after the start of the test. Test the eradication rate %.

In this test, it was found that the compounds of Production Examples (1), (2), (3), (4), and (6) exhibited superior action compared to the conventional technology, for example, in the LDloo-test (Japanese cockroach test). )(B 1at
tella germanica) F3 Ebibutan (Continued) Example C LT+on test on Diptera (]) 1ptera Test animal: House fly (Musca domestica)
) Number of test animals: 25 Solvent: acetone 25 parts by weight of active compound are taken up in 1.000 parts by volume of solvent. The resulting solution is further diluted with solvent to achieve the desired low concentration.

Pipette 2.5 m (2) of the active compound solution into the Petri dish. Place a filter paper approximately 9.5 cm in diameter on the bottom of the Petri dish. Leave the Petri dish open until the solvent has completely evaporated. The amount of active compound per m2 varies depending on the concentration of the active compound solution.

The above number of test animals is then placed in a Petri dish and the dish is covered with a glass lid.

Constantly check the condition of test animals. Eradication effect 100
Test the time required for %.

In this test, the compounds of Production Examples (1), (2), (3), (4) and (6) exhibited superior effects compared to the prior art.

Picture 9 Diptera (D 1pteren) (Musca
LT+oo test against domestica) = 63- Picture-p (continued) Active Compound Compound Compound F
3 SO□CF3 Example D Phaedon larva test Solvent 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is added to the above amount. Mixed with solvent and the above amount of emulsifier, the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea)
ica oleracea) were treated by soaking them in an active compound preparation of the desired concentration, and the larvae of the mustard beetle (Phaedon cochleariae) were treated by soaking them in an active compound preparation of the desired concentration.
ariae)) while the leaves are still moist.

After a specified period of time, the % eradication rate is tested. 100% means all larvae were killed; 0% means no larvae were killed.

In this test, superior effects compared to the conventional technology were found, for example, in Manufacturing Examples (1), (2), (3), (5),
It is produced by the compounds (6) and (7).

Human-p (insects that harm plants) Phedone-larvae-Test Active Compound Compound Compound
3 days later = 67- Maji 4 station (continued) SO2CF.

The main features and aspects of the invention are as follows.

1, Formula (I) (wherein R1 represents halogenoalkyl, Hal represents halogen, and R2, R3, R', R5 and R6 each independently represent hydrogen, halogen, cyano, nitro , alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxycarbonyl or -(X). -R7 group, where X is oxygen, sulfur, sulfinyl or sulfonyl, and n is the number 0 or l. , and R7 represents halogenoalkyl, provided that when R2-R6 simultaneously represent hydrogen, R
1 is trifluoromethyl free and Hal is fluorine free) 1-aryl-3-halogenoalkyl-4-halogeno-pyrazole.

2, R1 represents a linear or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, Hal represents fluorine, chlorine, bromine or iodine, and R2, R3 , R4, R5 and R6 are each independently hydrogen, halogen, cyano, nitro, alkyl, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkylsulfinyl, alkylsulfonyl, halogenoalkylsulfinyl, halogenoalkylsulfonyl or alkoxy carbonyl, which has 1 to 4 carbon atoms in each alkyl moiety
and, if appropriate, 1 to 9 identical or different halogen atoms, provided that if R2 to Rfi simultaneously contain hydrogen, R1 does not contain trifluoromethyl and Hal contains fluorine. 1-Aryl-3-halogenoalkyl-4-halogeno-pyrazole of formula (I) according to item 1 above, characterized in that:

3, R' is trifluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluoromethyl, trifluoroethyl, trifluorochloroethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl, and Hal is fluorine, chlorine or bromine, and R2, R3, R4, R1' and R6 are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl , n-1l-
1S- or t-butyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyl, ethoxytrifluoromethyl, dichlorofluoromethyl, cyfluorochloromethyl, difluoromethyl, pentafluoroethyl, trifluorochloroethyl,
trifluoroethyl, trifluorodichloroethyl, difluorochloroethyl or -X-R' group, where X is oxygen, sulfur, sulfinyl or sulfonyl, and R7 is trifluoromethyl, dichlorofluoromethyl,
Difluorochloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorochloroethyl, trichloromethyl or trifluorodichloroethyl, provided that R2-R6 are hydrogen at the same time. In case, R
1-aryl- of formula (I) according to paragraphs 1 and 2 above, characterized in that 1 does not contain trifluoromethyl and Hal does not contain fluorine.
3-halogenoalkyl-4-halogeno-pyrazole.

4, Formula (I) (wherein R1 represents halogenoalkyl, Hal represents halogen, and R2, R3, R4, R5 and R6 independently of each other,
hydrogen, halogen, cyano, nitro, alkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxycarbonyl or -(X), -R' group, where X is oxygen, sulfur, sulfinyl or sulfonyl, n represents the number O or 1, and R7 represents halogenoalkyl, provided that if R2-R6 simultaneously represent hydrogen, R1 shall not represent trifluoromethyl and Hal shall not represent fluorine. ) In producing l-aryl-3-halogenoalkyl-4-/10genopyrazole, a) formula (I[) (wherein R1 represents halogenoalkyl, Hal represents halogen, and The halogen-R-substituted acyl enol ether of R represents alkyl is diluted, if appropriate, with an arylhydrazine of the formula or b) N-aryl hydrazide halide of formula (IV) (wherein R1-R6 and Hat have the above meanings) is reacted with a compound of formula (V) Hal
-CH-CH-Hal (V) (wherein H
al represents a halogen, if appropriate in a diluent and if appropriate in the presence of an acid-binding agent, or C) with an alkene of formula (VI) in which R1-R6 has the abovementioned meaning) with a halogenating agent, if appropriate in a diluent, or d) of formula (■) R' (formula where R2-R6 have the above meanings) is reacted with an alkyne of formula (■) R'-C=C-Hal (■), if appropriate in a diluent. A method characterized by causing.

5. 1-aryl-3-halogenoalkyl- of formula (I)
An insecticide characterized by containing at least one type of 4-halogeno-pyrazole.

6. l-aryl-3-halogenoalkyl- of formula (I)
A method for controlling insects, which comprises applying 4-halogeno-pyrazole to insects and/or their environment.

7. 1-aryl-3- of formula (I) for controlling insects
Use of halogenoalkyl-4-halogeno-pyrazoles.

8. 1-aryl-3-halogenoalkyl- of formula (I)
A method for producing an insecticide, characterized in that 4-halogeno-pyrazole is mixed with a spreading agent and/or a surfactant.

Claims (1)

[Claims] 1. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents halogenoalkyl, Hal
represents halogen, and R^2, R^3, R^4, R^5 and R^6 each independently represent hydrogen, halogen, cyano, nitro, alkyl, alkylthio, alkylsulfinyl, Alkylsulfonyl, alkoxycarbonyl or -(X)_n
-R^7 group, where X represents oxygen, sulfur, sulfinyl or sulfonyl, n represents the number 0 or 1, and R^7 represents halogenoalkyl, provided that R^2 to R^6 At the same time represents hydrogen, R^1 does not represent trifluoromethyl and Ha
(l does not represent fluorine) 1-aryl-3-halogenoalkyl-4-halogeno-pyrazole. 2. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents halogenoalkyl, Hal
represents halogen, and R^2, R^3, R^4, R^5 and R^6 are each independently hydrogen, halogen, cyano, nitro, alkyl, alkylthio, alkylsulfinyl, alkyl Sulfonyl, alkoxycarbonyl or -(X)_n-R
represents a ^7 group, where X represents oxygen, sulfur, sulfinyl or sulfonyl, n represents the number 0 or 1, and R^7 represents halogenoalkyl, provided that R^2 to R^6 are simultaneously When representing hydrogen, R
^1 does not represent trifluoromethyl and Hal does not represent fluorine) In producing 1-aryl-3-halogenoalkyl-4-halogeno-pyrazole, a) Formula (II) ▲ Formula, There are chemical formulas, tables, etc.▼ (In the formula, R^1 represents halogenoalkyl, Hal
represents a halogen, and R represents an alkyl) The halogen-substituted acyl enol ether of the formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^2 ~ R^ 6 has the above meaning), if appropriate in a diluent, or b) formula (IV) ▲ any mathematical formula, chemical formula, table etc. ▼ (IV) (wherein R^1 to R^6 and Hal have the above-mentioned meanings).
-CH=CH-Hal(V) (wherein Hal represents a halogen) with an alkene, if appropriate in a diluent and if appropriate in the presence of an acid-binding agent, or c ) Formula (VI) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (VI) (In the formula, R^1 to R^6 have the above meanings) 1-aryl-3-halogenoalkyl-pyrazole is replaced with a halogen or d) Formula (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) (wherein R^2 to R^6 are the above) ) with the alkyne of formula (VIII) R^1-C≡C-Hal (VIII), where R^1 and Hal have the above meanings. , if appropriate in a diluent. 3. An insecticide containing at least one 1-aryl-3-halogenoalkyl-4-halogenopyrazole of formula (I).